Plastic lenses and glass lenses often perform the same function in optical systems, such as in cameras, microscopes, telescopes, and opthalmic wear. The two main attributes that separate plastic lenses from glass lenses are cost and optical stability. Plastic lenses typically cost 1/100th the price of a similar glass lens while the stability of the refractive index of a glass lens with respect to temperature and humidity is typically 100 times better than that of a plastic lens.
The difference in cost is due largely to the difference in manufacturing processes that are required for the two materials and the relative temperatures that the materials must be formed at. Plastic lenses are typically produced at 230° C. using injection molding at cycle times that are 10 times faster than glass lenses that are largely produced by grinding and polishing or compression molding at 625° C. Grinding and polishing are labor intensive while the high temperatures that glass must be formed at requires expensive mold materials and extensive maintenance costs.
In contrast, the difference in optical stability between plastic and glass is due to differences in their basic material properties. This difference in optical stability results in substantially more variation in focus and image quality in articles such as cameras when plastic lenses are used in place of glass. What is desired, and a remaining challenge in the art, is a material with the optical stability of glass that processes like a plastic.
While optical plastic materials such as cyclic olefins greatly improve the refractive index stability with respect to humidity, improving the refractive index stability with respect to temperature has remained an opportunity. A study on the competing fundamental material characteristics that determine the sign and the magnitude of the dn/dT of glasses is available, for instance, by Lucien Prod'homme, “A New Approach To The Thermal Change In The Refractive Index Of Glasses,” Physics and Chemistry of Glasses, Vol. 1, No. 4, August 1960. There are two competing effects that determine the dn/dT in glasses. These are the density change, which produces a negative dn/dT and the electronic polarizability, which produces a positive dn/dT. The net dn/dT in a glass material depends on which effect dominates. In optical plastics however, the electronic polarizability is very small compared to the density change so that all unfilled plastic materials have negative dn/dT values. Nonetheless, the article by Prod'homme does identify the possibility of using glass-like fillers with positive dn/dT values to substantially alter the dn/dT of a glass-plastic composite material.
Nanoparticulate fillers have been used to modify the index of refraction of optical plastics. By using a nanoparticulate filler small enough that it is well below the wavelength of visible light (400–700 nm), light scattering from the nanoparticles is reduced and the filled plastic can remain transparent. WIPO Patent No. WO97/10527 by John S. Toeppen, published Mar. 20, 1997, titled “Structured Index Optics And Ophthalmic Lenses For Vision Correction” describes the use of nanoparticles to increase the refractive index of plastics for opthalmic applications. In addition, technical references that describe the addition of nanoparticles to increase the refractive index of plastics include: “Optical And Thermomechanical Investigations On Thermoplastic Nanocomposites With Surface Modified Silica Nanoparticles” by C. Becker et al., SPIE Conference, Vol. 3469, pp. 88–98, July 1998; and “Tantalum Oxide Nanomers For Optical Applications” by B. Braune et al., SPIE Conference, Vol. 3469, pp. 124–132, July 1998. While these references disclose the use of nanoparticles to modify refractive index of optical plastics they do not discuss the issue of refractive index stability with respect to temperature which requires a different set of characteristics in the nanoparticle.
U.S. Pat. No. 6,441,077 titled “Polysulfone Nanocomposite Optical Plastic Article And Method Of Making Same” issued Aug. 27, 2002 to Border et al., discloses the use of a nanoparticulate filler in an optical plastic, where the nanoparticulate filler has been chosen with a positive dn/dT to counteract the negative dn/dT of the plastic host material such that the overall dn/dT of the nanocomposite has a substantially reduced magnitude of dn/dT, where dn is the change in refractive index of the nanocomposite material produced by a change in temperature dT.
In experiments and computer modeling done at Eastman Kodak, it has been noted that the addition of even very small nanoparticles (10–40 nm) into plastic host materials can lead to low level light scattering or haze in the nanocomposite material which limits light transmission to less than 90%. The haze is especially noticeable at loadings greater than 10% of the nanoparticles in the plastic host material, such as is required to substantially improve the thermal stability of the refractive index (reduced dn/dT) of the nanocomposite material. Haze is also particularly noticeable if the refractive index of the nanoparticles is substantially different from the refractive index of the plastic host material.
While there have been several attempts to modify properties of plastics using nanoparticles, none of these attempts have proven successful in producing optical plastic articles with improved temperature stable optical properties while retaining important processing characteristics and low levels of haze.
U.S. Pat. No. 5,252,441 titled “Transparent Magnetic Recording Layers And Photographic Elements Containing The Same” issued Oct. 12, 1993 to James et al. and U.S. Pat. No. 5,217,804 titled “Magnetic Particles” issued Jun. 8, 1993 to James et al. disclose a coating technique for magnetic particles that reduces the extinction coefficient by applying coatings to high refractive index magnetic particles thereby reducing the haze of the material. Examples show how the coating of the particles with a low refractive index layer reduced the optical density (haze). However, James et al. do not contemplate the impact of the particles or the coating material on the overall thermal stability of the refractive index of the nanocomposite material.
U.S. Pat. No. 5,985,173 titled “Phosphors Having A Semiconductor Host Surrounded By A Shell” issued Nov. 16, 1999 to Gray et al. describes a technique for applying a shell coating to doped zinc sulfide particles. However, the goal of this invention is related to establishing a bandgap to modify the surface electronic state of the doped host particle. This invention does not address the transparency of the nanocomposite material.
Likewise, in WIPO Publication Number WO99/21934 by Mulvaney et al., published May 6, 1999 and titled “Stabilized Particles And Methods Of Preparation And Use Thereof,” Mulvaney et al. disclose a method for stabilizing nanoparticles by coating them with an insulating, semiconducting and/or metallic coating. While Mulvaney et al., do disclose techniques for applying coatings to nanoparticles and some of the materials presented do have positive dn/dT values such cadmium sulfide, zinc sulfide, zinc selenide, silica, and alumina, Mulvaney et al. only disclose the use of coated nanoparticles to improve fluorescence, electrofluorescence, and detection of an analyte. Mulvaney et al. do not anticipate the use of coated nanoparticles to modify the optical performance of optical articles such as lenses to improve thermal stability (dn/dT) of the refractive index. In fact, in Example F. on page 19, line 6, Mulvaney et al. make the statement that “the optical properties of the CdS particles are not significantly altered by silica deposition.”
Therefore, a need persists in the art for optical plastic articles, such as lenses, and a method of making same that have improved temperature stable optical properties with low levels of haze.